U.S. patent application number 15/481488 was filed with the patent office on 2017-10-12 for liquid acidic hard surface cleaning compositions having improved shine.
The applicant listed for this patent is The Procter & Gamble Company. Invention is credited to Anna ASMANIDOU, Gloria DI CAPUA, Aaron FLORES-FIGUEROA, Frank HULSKOTTER, Martin RUEBENACKER, Stefano SCIALLA, James Robert TINLIN.
Application Number | 20170292092 15/481488 |
Document ID | / |
Family ID | 55701875 |
Filed Date | 2017-10-12 |
United States Patent
Application |
20170292092 |
Kind Code |
A1 |
ASMANIDOU; Anna ; et
al. |
October 12, 2017 |
LIQUID ACIDIC HARD SURFACE CLEANING COMPOSITIONS HAVING IMPROVED
SHINE
Abstract
Liquid acidic hard surface cleaning composition comprising
certain copolymers provide good limescale removal and long lasting
shine to a broad range of surfaces. Moreover, when formulated with
suitable acid systems, they also provide improved surface safety
over more delicate surfaces.
Inventors: |
ASMANIDOU; Anna; (Brussels,
BE) ; DI CAPUA; Gloria; (Ardea, IT) ;
FLORES-FIGUEROA; Aaron; (Mannheim, DE) ; HULSKOTTER;
Frank; (Schwalbach am Taunus, DE) ; RUEBENACKER;
Martin; (Altrip, DE) ; SCIALLA; Stefano;
(Rome, IT) ; TINLIN; James Robert; (Brussels,
BE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Procter & Gamble Company |
15481488 |
OH |
US |
|
|
Family ID: |
55701875 |
Appl. No.: |
15/481488 |
Filed: |
April 7, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D 3/2079 20130101;
C11D 3/044 20130101; C11D 3/3776 20130101; C11D 3/2086 20130101;
C11D 3/3769 20130101; C11D 3/3757 20130101; C11D 3/042 20130101;
C11D 11/0023 20130101 |
International
Class: |
C11D 3/37 20060101
C11D003/37; C11D 3/20 20060101 C11D003/20; C11D 3/04 20060101
C11D003/04; C11D 11/00 20060101 C11D011/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 8, 2016 |
EP |
16 164 580.9 |
Claims
1. A liquid acidic hard surface cleaning composition having a pH of
from about 0.1 to about 6.5 and comprising a copolymer, wherein the
copolymer comprises: i. from about 60 to about 99% by weight of at
least one monoethylenically unsaturated polyalkylene oxide monomer
of the formula I (monomer A) ##STR00005## in which the variables
have the following meanings: X is --CH.sub.2-- or --CO--, if Y is
--0--; is --CO--, if Y is --NH--; Y is --O-- or --NH--; R.sub.1 is
hydrogen or methyl; R.sub.2 are identical or different
C2-C6-alkylene radicals; R.sub.3 is H or C1-C4 alkyl; n is an
integer from about 5 to about 100, ii. from about 1 to about 40% by
weight of at least one quaternized nitrogen-containing monomer,
selected from the group consisting of at least one of the monomers
of the formula IIa to IId (monomer B) ##STR00006## in which the
variables have the following meanings: R is C1-C4 alkyl or benzyl;
R' is hydrogen or methyl; Y is --O-- or --NH--; A is C1-C6
alkylene; X.sup.- is halide, C1-C4-alkyl sulfate,
C1-C4-alkylsulfonate and C1-C4-alkyl carbonate, iii. from about 0
to about 15% by weight of at least one anionic monoethylenically
unsaturated monomer (monomer C), and iv. from about 0 to about 30%
by weight of at least one other non-ionic monoethylenically
unsaturated monomer (monomer D), wherein: if monomer C is present,
the molar ratio of monomer B to monomer C is greater than about 1,
and the copolymer has a weight average molecular weight (Mw) from
about 20,000 g/mol to about 500,000 g/mol.
2. The composition according to claim 1, in which the variables of
monomer (A) have the following meanings: X is --CO--; Y is --O--;
R.sub.1 is hydrogen or methyl; R.sub.2 is ethylene, linear or
branched propylene or mixtures thereof; R.sub.3 is methyl; n is an
integer from about 5 to about 100.
3. The hard surface composition according to claim 2, wherein
monomer A of the copolymer, n is an integer from about 20 to about
50.
4. The hard surface cleaning composition according to claim 1,
wherein the copolymer comprises from about 60 to about 99% by
weight of monomer A and from about 1 to about 20% by weight of
monomer B, from about 0 to about 15% by weight of monomer C, and
from about 0 to about 20% by weight of monomer D, and where monomer
C is present, the weight ratio of monomer B to monomer C is greater
than about 1.
5. The hard surface cleaning composition according to claim 4,
wherein the weight ratio of monomer B to monomer C of the copolymer
is greater than about 2.5.
6. The composition according to claim 1, wherein monomer (B) is a
salt of 3-methyl-1-vinylimidazolium.
7. The hard surface cleaning composition according to claim 1
wherein monomer A is methylpolyethylene glycol (meth)acrylate.
8. The hard surface cleaning composition according to claim 1
wherein monomer A is methylpolyethylene glycol (meth)acrylate and
wherein monomer B is a salt of 3-methyl-1-vinylimidazolium, and
monomer D is N-vinylimidazole.
9. The composition according to claim 1, wherein said composition
further comprises an anionic polymeric thickener.
10. The composition according to claim 1, wherein said composition
has a pH of from about 1 to about 6.
11. The composition according to claim 1, wherein the composition
comprises acid an acid system, the acid system comprising acid
selected from the group consisting of: citric acid, formic acid,
acetic acid, maleic acid, lactic acid, glycolic acid, succinic
acid, glutaric acid, adipic acid, sulphamic acid, sulphuric acid,
hydrochloric acid, phosphoric acid, nitric acid, methane sulphonic
acid, and mixtures thereof.
12. The composition according to claim 9, wherein said composition
comprises the acid system at a level of from about 0.01% to about
15% by weight of the total composition.
13. The composition according to claim 1, wherein said composition
further comprises a nonionic surfactant.
14. The composition according to claim 13, wherein the nonionic
surfactant is the condensation product of ethylene and/or propylene
oxide with an alcohol having a straight alkyl chain comprising from
about 6 to about 22 carbon atoms, wherein the degree of
ethoxylation/propoxylation is from about 1 to about 15, or mixtures
thereof.
15. The composition according to claim 1, wherein said composition
further comprises one or more ingredients selected from the group
of: vinylpyrrolidone homopolymer or copolymer; polysaccharide
polymer; solvents; anionic surfactants; cationic surfactants;
amphoteric surfactants; zwitterionic surfactants; radical
scavengers; caustics; perfumes; and dyes; and mixtures thereof.
16. The composition according to claim 1, wherein said composition
further comprises an alkaline material.
17. The composition according to claim 16, wherein the alkaline
material is selected from the group consisting of sodium hydroxide,
potassium hydroxide, lithium hydroxide, the alkali metal oxides
such as sodium and/or potassium oxide or mixtures thereof,
monoethanolamine, triethanolamine, ammonia, ammonium carbonate and,
choline base and mixtures thereof.
18. The composition according to claim 17, wherein the alkaline
material is selected from the group consisting of sodium hydroxide
or potassium hydroxide.
19. A process of removing limescale from a hard surface or an
object, comprising the steps of: applying a liquid acidic hard
surface cleaning composition according to claim 1 onto said
hard-surface or said object; leaving said composition on said
hard-surface or said object to act; optionally wiping said
hard-surface or object and/or providing mechanical agitation, and
then rinsing said hard-surface or said object.
20. A process of removing limescale from an object, comprising the
step of immersing said object in a bath comprising a composition
according to claim 1, leaving said object in said bath for said
composition to act, and then rinsing said object.
Description
TECHNICAL FIELD
[0001] The present invention relates to acidic liquid compositions
for cleaning a variety of hard surfaces such as hard surfaces found
in around the house, such as bathrooms, toilets, garages,
driveways, basements, gardens, kitchens, etc. More specifically,
the compositions of the present invention deliver good limescale
removal performance (i.e., removal of pure limescale deposits
and/or limescale-containing soils) and good shine, whilst having a
good surface safety profile on the treated surface.
BACKGROUND OF THE INVENTION
[0002] Liquid compositions for cleaning limescale from
hard-surfaces have been disclosed in the art. Limescale deposits,
are formed due to the fact that tap water contains a certain amount
of solubilised ions, which upon water evaporation eventually
deposit as salts such as calcium carbonate on hard surfaces, which
are frequently in contact with water. The visible limescale
deposits result in an unaesthetic aspect of the surfaces. The
limescale formation and deposition phenomenon is even more acute in
places where water is particularly hard. Furthermore, limescale
deposits are prone to combination with other types of soils, such
as soap scum or grease, and can lead to the formation of
limescale-soil mixture deposits (limescale-containing soils). The
removal of limescale deposits and limescale-containing soils is
herein in general referred to as "limescale removal" or "removing
limescale".
[0003] Films and streaks may be left which results in poor shine,
and an impression that the surface is not yet sufficiently clean.
Surface active polymers, such as polyvinylpyrrolidone and
polycarboxylates have been formulated into acidic cleaners to
improve shine on ceramic surfaces. However, such polymers have been
found to be less effective on other surfaces, especially those
found in kitchens and the like.
[0004] More delicate materials are also often found in kitchens
than the ceramics that are typically found in bathrooms and the
like. Such surfaces include polymers, including formica.TM., vinyl,
melamine, and other polymeric materials, in addition to stainless
steels, glass, brass, and other metals. Hence, it is desirable to
formulate the acid hard surface cleaning compositions which are
suitable for such surfaces, while also leaving the surfaces
pleasantly shiny.
[0005] In addition, surface active polymers can be challenging to
formulate stably into acidic compositions.
[0006] As such, a need remains for stable hard surface cleaning
compositions which are more suitable for removing limescale from
kitchen surfaces, especially where grease stains are present, while
also providing long lasting shine.
[0007] WO 2004/018599 describes acidic hard surface cleaning
compositions comprising an acid or a mixture thereof. EP0666306 A1
and EP0666305 A1 describe liquid compositions suitable for removing
limescale from hard surfaces comprising maleic acid in combination
with a second acid. EP2206766 A1 relates to a liquid acidic hard
surface cleaning composition having a pH of from 2 to 2.9 and
comprising formic acid and an alkaline material. WO2005/052107
relates to laundry compositions having copolymers containing
polyalkylene oxide groups and quanternary nitrogen atoms and a
surfactant system.
SUMMARY OF THE INVENTION
[0008] The present invention relates to a liquid acidic hard
surface cleaning composition having a pH of from 0.1 to 6.5 and
comprising a copolymer, as described in claim 1. The present
invention further relates to a method of reducing the drying time
of treated hard surfaces. The present invention further relates to
the use of the copolymer for reducing the drying time of treated
hard surfaces.
DETAILED DESCRIPTION OF THE INVENTION
[0009] The present compositions provide good limescale removal and
long lasting shine over a wide range of surfaces. When formulated
with the preferred acid systems, the acidic cleaning compositions
provide good cleaning and long lasting shine, with little or no
damage to delicate surfaces.
[0010] The Liquid Acidic Hard Surface Cleaning Composition
[0011] The compositions according to the present invention are
designed as hard surfaces cleaners. The compositions according to
the present invention are liquid compositions (including gels) as
opposed to a solid or a gas.
[0012] The liquid acidic hard surface cleaning compositions
according to the present invention are preferably aqueous
compositions. Therefore, they may comprise from 70% to 99% by
weight of the total composition of water, preferably from 75% to
95% and more preferably from 80% to 95%.
[0013] The liquid compositions of the present invention are acidic.
Therefore they have a pH of less than 7. Preferably, the
composition has a pH of from 1 to 6, more preferably from 2.0 to
2.5, still more preferably from 2.1 to 2.5, and most preferably
from 2.1 to 2.4. The pH of the cleaning compositions is measured at
25.degree. C.
[0014] Thus, the compositions comprise an acid system. Typically,
the acid system may comprise any organic or inorganic acid
well-known to those skilled in the art, or a mixture thereof. In
preferred embodiments, the acid system comprises acids selected
from the group consisting of: citric acid, formic acid, acetic
acid, maleic acid, lactic acid, glycolic acid, succinic acid,
glutaric acid, adipic acid, sulphamic acid, sulphuric acid,
hydrochloric acid, phosphoric acid, nitric acid, methane sulphonic
acid, and mixtures thereof, preferably acids selected from the
group consisting of: citric acid, formic acid, acetic acid, lactic
acid, phosphoric acid, and mixtures thereof.
[0015] The composition preferably comprises the acid system at a
level of from 0.01% to 15%, preferably from 0.5% to 10%, more
preferably from 2% to 8%, most preferably from 4% to 7.5% by weight
of the total composition.
[0016] Formic acid has been found to provide excellent limescale
removal performance, in combination with improved surface safety,
especially for surfaces which are prone to corrosion. For improved
surface safety, especially of more delicate surfaces, the
composition preferably comprises formic acid as part of the acid
system. In order to achieve the desired pH, the compositions of the
present invention may comprise from 0.01% to 15%, preferably from
0.5% to 10%, more preferably from 1% to 8%, even more preferably
from 1% to 6%, still more preferably 1% to 4%, yet more preferably
1% to 3%, yet still more preferably 2% to 3% by weight of the total
composition of formic acid.
[0017] Lactic acid can be used as part of the acid system,
especially where antimicrobial or disinfecting benefits are
desired. Such compositions may comprise up to 10% by weight of the
total composition of lactic acid, preferably from 0.1% to 6%, more
preferably from 0.2% to 4%, even more preferably from 0.2% to 3%,
and most preferably from 0.5% to 2%.
[0018] The compositions of the present invention may comprise from
0.1 to 30%, preferably from 2% to 20%, more preferably from 3% to
15%, most preferably from 3% to 10% by weight of the total
composition of acetic acid. In an alternative embodiment herein,
the compositions of the present invention may comprise from 0.1 to
5%, preferably from 0.1% to 3%, more preferably from 0.1% to 2%,
most preferably from 0.5% to 2% by weight of the total composition
of acetic acid.
[0019] The compositions of the present invention may comprise from
0.1 to 30%, preferably from 1% to 20%, more preferably from 1.5% to
15%, most preferably from 2% to 10% by weight of the total
composition of citric acid.
[0020] The compositions herein can comprise an alkaline material.
The alkaline material may be present to trim the pH and/or maintain
the pH of the compositions according to the present invention.
Examples of alkaline material are sodium hydroxide, potassium
hydroxide and/or lithium hydroxide, and/or the alkali metal oxides
such, as sodium and/or potassium oxide or mixtures thereof and/or
monoethanolamine and/or triethanolamine Other suitable bases
include ammonia, ammonium carbonate, choline base, etc. Preferably,
source of alkalinity is sodium hydroxide or potassium hydroxide,
preferably sodium hydroxide.
[0021] Typically the amount of alkaline material is of from 0.001%
to 20% by weight, preferably from 0.01% to 10% and more preferably
from 0.05% to 3% by weight of the composition.
[0022] Despite the presence of alkaline material, if any, the
compositions herein would remain acidic compositions.
[0023] The compositions herein may have a water-like viscosity. By
"water-like viscosity" it is meant herein a viscosity that is close
to that of water. Preferably the liquid acidic hard surface
cleaning compositions herein have a viscosity of up to 50 cps at 60
rpm, more preferably from 0 cps to 30 cps, yet more preferably from
0 cps to 20 cps and most preferably from 0 cps to 10 cps at 60
rpm.sup.1 and 20.degree. C. when measured with a Brookfield digital
viscometer model DV II, with spindle 2.
[0024] In other embodiments, the compositions herein are thickened
compositions. Thus, the liquid acidic hard surface cleaning
compositions herein preferably have a viscosity of from 50 cps to
5000 cps at 20 s.sup.-1, more preferably from 50 cps to 2000 cps,
yet more preferably from 50 cps to 1000 cps and most preferably
from 50 cps to 500 cps at 20 s.sup.-1 and 20.degree. C. when
measured with a Rheometer, model AR 1000 (Supplied by TA
Instruments) with a 4 cm conic spindle in stainless steal,
2.degree. angle (linear increment from 0.1 to 100 sec.sup.-1 in
max. 8 minutes). Preferably, the thickened compositions according
to this specific embodiment are shear-thinning compositions. The
thickened liquid acidic hard surface cleaning compositions herein
preferably comprise a thickener, more preferably a polysaccharide
polymer (as described herein below) as thickener, still more
preferably a gum-type polysaccharide polymer thickener and most
preferably Xanthan gum.
[0025] The Copolymer:
[0026] The hard surface cleaning composition of the invention
preferably comprises from 0.01% to 10%, more preferably from 0.05%
to 5%, yet more preferably from 0.1% to 3%, most preferably from
0.15 to 1% by weight of the cleaning composition, of the
copolymer.
[0027] The copolymer comprises monomers selected from the group
comprising monomers of formula (I) (Monomer A) and monomers of
formula (IIa-IId) (Monomer B). The copolymer comprises from 60 to
99%, preferably from 70 to 95% and especially from 80 to 90% by
weight of at least one monoethylenically unsaturated polyalkylene
oxide monomer of the formula (I) (monomer A)
##STR00001##
wherein Y of formula (I) is selected from --O-- and --NH--; if Y of
formula (I) is --O--, X of formula (I) is selected from
--CH.sub.2-- or --CO--, if Y of formula (I) is --NH--, X of formula
(I) is --CO--; R.sup.1 of formula (I) is selected from hydrogen,
methyl, and mixtures thereof; R.sup.2 of formula (I) is
independently selected from linear or branched
C.sub.2-C.sub.6-alkylene radicals, which may be arranged blockwise
or randomly; R.sup.3 of formula (I) is selected from hydrogen,
C.sub.1-C.sub.4-alkyl, and mixtures thereof; n of formula (I) is an
integer from 5 to 100, preferably from 10 to 70 and more preferably
from 20 to 50.
[0028] The copolymer comprises from 1 to 40%, preferably from 2 to
30% and especially from 5 to 20% by weight of at least one
quaternized nitrogen-containing monoethylenically unsaturated
monomer of formula (IIa-IId) (monomer B).
[0029] The monomers are selected such that the copolymer has a
weight average molecular weight (M.sub.w) of from 20,000 to 500,000
g/mol, preferably from greater than 25,000 to 150,000 g/mol and
especially from 30,000 to 80,000 g/mol.
[0030] The copolymer preferably has a net positive charge at a pH
of 5 or above.
[0031] The copolymer for use in the present invention may further
comprise monomers C and/or D.
[0032] Monomer C may comprise from 0% to 15%, preferably from 0 to
10% and especially from 1 to 7% by weight of the copolymer of an
anionic monoethylenically unsaturated monomer.
[0033] Monomer D may comprise from 0% to 40%, preferably from 1 to
30% and especially from 5 to 20% by weight of the copolymer of
other non-ionic monoethylenically unsaturated monomers.
[0034] Preferred copolymers according to the invention comprise, as
copolymerized Monomer A, monoethylenically unsaturated polyalkylene
oxide monomers of formula (I) in which Y of formula (I) is --O--; X
of formula (I) is --CO--; R.sup.1 of formula (I) is hydrogen or
methyl; R.sup.2 of formula (I) is independently selected from
linear or branched C.sub.2-C.sub.4-alkylene radicals arranged
blockwise or randomly, preferably ethylene, 1,2- or 1,3-propylene
or mixtures thereof, particularly preferably ethylene; R.sup.3 of
formula (I) is methyl; and n is an integer from 20 to 50.
[0035] Monomer A
[0036] A monomer A for use in the copolymer of the present
invention may be, for example: [0037] (a) reaction products of
(meth)acrylic acid with polyalkylene glycols which are not
terminally capped, terminally capped at one end by alkyl radicals;
and [0038] (b) alkenyl ethers of polyalkylene glycols which are not
terminally capped or terminally capped at one end by alkyl
radicals.
[0039] Preferred monomer A is the (meth)acrylates and the allyl
ethers, where the acrylates and primarily the methacrylates are
particularly preferred. Particularly suitable examples of the
monomer A are: [0040] (a) methylpolyethylene glycol (meth)acrylate
and (meth)acrylamide, methylpolypropylene glycol (meth)acrylate and
(meth)acrylamide, methylpolybutylene glycol (meth)acrylate and
(meth)acrylamide, methylpoly(propylene oxide-co-ethylene oxide)
(meth)acrylate and (meth)acrylamide, ethylpolyethylene glycol
(meth)acrylate and (meth)acrylamide, ethylpolypropylene glycol
(meth)acrylate and (meth)acrylamide, ethylpolybutylene glycol
(meth)acrylate and (meth)acrylamide and ethylpoly(propylene
oxide-co-ethylene oxide) (meth)acrylate and (meth)acrylamide, each
with 5 to 100, preferably 10 to 70 and particularly preferably 20
to 50, alkylene oxide units, where methylpolyethylene glycol
acrylate is preferred and methylpolyethylene glycol methacrylate is
particularly preferred; [0041] (b) ethylene glycol allyl ethers and
methylethylene glycol allyl ethers, propylene glycol allyl ethers
and methylpropylene glycol allyl ethers each with 5 to 100,
preferably 10 to 70 and particularly preferably 20 to 50, alkylene
oxide units.
[0042] The proportion of Monomer A in the copolymer according to
the invention is 60% to 99% by weight, preferably 70% to 95%, more
preferably from 80% to 90% by weight of the copolymer.
[0043] Monomer B
[0044] A monomer B that is particularly suitable for the copolymer
of the invention includes the quaternization products of
1-vinylimidazoles, of vinylpyridines, of (meth)acrylic esters with
amino alcohols, in particular
N,N-di-C.sub.1-C.sub.4-alkylamino-C.sub.2-C.sub.6-alcohols, of
amino-containing (meth)acrylamides, in particular
N,N-di-C.sub.1-C.sub.4-alkyl-amino-C.sub.2-C.sub.6-alkylamides of
(meth)acrylic acid, and of diallylalkylamines, in particular
diallyl-C.sub.1-C.sub.4-alkylamines
[0045] Suitable monomers B have the formula IIa to IId:
##STR00002##
wherein R of formula IIa to IId is selected from
C.sub.1-C.sub.4-alkyl or benzyl, preferably methyl, ethyl or
benzyl; R' of formula a is selected from hydrogen or methyl; Y of
formula IIc is selected from --O-- or --NH--; A of formula IIc is
selected from C.sub.1-C.sub.6-alkylene, preferably straight-chain
or branched C.sub.2-C.sub.4-alkylene, in particular 1,2-ethylene,
1,3- and 1,2-propylene or 1,4-butylene; X-- of formula IIa to IId
is selected from halide, such as iodide and preferably chloride or
bromide, C.sub.1-C.sub.4-alkyl sulfate, preferably methyl sulfate
or ethyl sulfate, C.sub.1-C.sub.4-alkylsulfonate, preferably
methylsulfonate or ethylsulfonate, C.sub.1-C.sub.4-alkyl carbonate;
and mixtures thereof.
[0046] Specific examples of preferred monomer B that may be
utilized in the present invention are: [0047] (a)
3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium
methyl sulfate, 3-ethyl-1-vinylimidazolium ethyl sulfate,
3-ethyl-1-vinylimidazolium chloride and 3-benzyl-1-vinylimidazolium
chloride; [0048] (b) 1-methyl-4-vinylpyridinium chloride,
1-methyl-4-vinylpyridinium methyl sulfate and
1-benzyl-4-vinylpyridinium chloride; [0049] (c)
3-methacrylamido-N,N,N-trimethylpropan-1-aminium chloride,
3-acryl-N,N,N-trimethylpropan-1-aminium chloride,
3-acryl-N,N,N-trimethylpropan-1-aminium methylsulfate,
3-methacryl-N,N,N-trimethylpropan-1-aminium chloride,
3-methacryl-N,N,N-trimethylpropan-1-aminium methylsulfate,
2-acrylamido-N,N,N-trimethylethan-1-aminium chloride,
2-acryl-N,N,N-trimethylethan-1-aminium chloride,
2-acryl-N,N,N-trimethylethan-1-aminium methyl sulfate,
2-methacryl-N,N,N-trimethylethan-1-aminium chloride,
2-methacryl-N,N,N-trimethylethan-1-aminium methyl sulfate,
2-acryl-N,N-dimethyl-N-ethylethan-1-aminium ethylsulfate,
2-methacryl-N,N-dimethyl-N-ethylethan-1-aminium ethylsulfate, and
[0050] (d) dimethyldiallylammonium chloride and
diethyldiallylammonium chloride.
[0051] A preferred monomer B is selected from 3-methyl-
1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl
sulfate, 3-methacryl-N,N,N-trimethylpropan-1-aminium chloride,
2-methacryl-N,N,N-trimethylethan-1-aminium chloride,
2-methacryl-N,N-dimethyl-N-ethylethan-1-aminium ethylsulfate, and
dimethyldiallylammonium chloride.
[0052] The copolymer according to the invention comprises 1% to 40%
by weight, preferably 2% to 30%, and especially preferable from 5
to 20% by weight of the copolymer, of Monomer B. The weight ratio
of Monomer A to Monomer B is preferably equal to or greater than
2:1, preferably 3:1 to 5:1.
[0053] Monomer C
[0054] As optional components of the copolymer of the present
invention, monomers C and D may also be utilized. Monomer C is
selected from anionic monoethylenically unsaturated monomers.
Suitable monomer C may be selected from: [0055] (a)
.alpha.,.beta.-unsaturated monocarboxylic acids which preferably
have 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid,
2-methylenebutanoic acid, crotonic acid and vinylacetic acid,
preference being given to acrylic acid and methacrylic acid; [0056]
(b) unsaturated dicarboxylic acids, which preferably have 4 to 6
carbon atoms, such as itaconic acid and maleic acid, anhydrides
thereof, such as maleic anhydride; [0057] (c) ethylenically
unsaturated sulfonic acids, such as vinylsulfonic acid,
acrylamido-propanesulfonic acid, methallylsulfonic acid,
methacrylsulfonic acid, m- and p-styrenensulfonic acid,
(meth)acrylamidomethanesulfonic acid,
(meth)acrylamidoethanesulfonic acid,
(meth)acrylamidopropanesulfonic acid,
2-(meth)acrylamido-2-methylpropanesulfonic acid,
2-acrylamido-2-butanesulfonic acid,
3-methacrylamido-2-hydroxypropanesulfonic acid, methanesulfonic
acid acrylate, ethanesulfonic acid acrylate, propanesulfonic acid
acrylate, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic
acid and 1-allyloxy-2-hydroxypropanesulfonic acid; and [0058] (d)
ethylenically unsaturated phosphonic acids, such as vinylphosphonic
acid and m- and p-styrenephosphonic acid.
[0059] The anionic Monomer C can be present in the form of water
soluble free acids or in water-soluble salt form, especially in the
form of alkali metal and ammonium, in particular alkylammonium,
salts, and preferred salts being the sodium salts.
[0060] A preferred Monomer C may be selected from acrylic acid,
methacrylic acid, maleic acid, vinylsulfonic acid,
2-(meth)acrylamido-2-methylpropanesulfonic acid and vinylphosphonic
acid, particular preference being given to acrylic acid,
methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid.
[0061] The proportion of monomer C in the copolymer of the
invention can be up to 15% by weight, preferably from 1% to 5% by
weight of the copolymer.
[0062] If monomer C is present in the copolymer of the present
invention, then , the molar ratio of monomer B to monomer C is
greater than 1. The weight ratio of Monomer A to monomer C is
preferably equal to or greater than 4:1, more preferably equal to
or greater than 5:1. Additionally, the weight ratio of monomer B to
monomer C is equal or greater than 2:1, and even more preferable
from 2.5:1
[0063] Monomer D
[0064] As an optional component of the copolymer of the present
invention, monomer D may also be utilized. Monomer D is selected
from nonionic monoethylenically unsaturated monomers selected from:
[0065] (a) esters of monoethylenically unsaturated
C.sub.3-C.sub.6-carboxylic acids, especially acrylic acid and
methacrylic acid, with monohydric C.sub.1-C.sub.22-alcohols, in
particular C.sub.1-C.sub.16-alcohols; and hydroxyalkyl esters of
monoethylenically unsaturated C.sub.3-C.sub.6-carboyxlic acids,
especially acrylic acid and methacrylic acid, with divalent
C.sub.2-C.sub.4-alcohols, such as methyl (meth)acrylate, ethyl
(meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate,
tert-butyl (meth)acrylate, ethylhexyl (meth)acrylate, decyl
(meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate,
cetyl (meth)acrylate, palmityl (meth)acrylate and stearyl
(meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl
(meth)acrylate and hydroxybutyl (meth)acrylate; [0066] (b) amides
of monoethylenically unsaturated C.sub.3-C.sub.6-carboxylic acids,
especially acrylic acid and methacrylic acid, with
C.sub.1-C.sub.12-alkylamines and di(C.sub.1-C.sub.4-alkyl)amines,
such as N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide,
N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide,
N-tert-butyl(meth)acrylamide, N-tert-octyl(meth)acrylamide and
N-undecyl(meth)acrylamide, and (meth)acrylamide; [0067] (c) vinyl
esters of saturated C.sub.2-C.sub.30-carboxylic acids, in
particular C.sub.2-C.sub.14-carboxylic acids, such as vinyl
acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate
and vinyl laurate; [0068] (d) vinyl C.sub.1-C.sub.30-alkyl ethers,
in particular vinyl C.sub.1-C.sub.18-alkyl ethers, such as vinyl
methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl
isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl
2-ethylhexyl ether and vinyl octadecyl ether; [0069] (e)
N-vinylamides and N-vinyllactams, such as N-vinylformamide,
N-vinyl-N-methyl-formamide, N-vinylacetamide,
N-vinyl-N-methylacetamide, N-vinylimidazol, N-vinylpyrrolidone,
N-vinylpiperidone and N-vinylcaprolactam; [0070] (f) aliphatic and
aromatic olefins, such as ethylene, propylene,
C.sub.4-C.sub.24-.alpha.-olefins, in particular
C.sub.4-C.sub.16-.alpha.-olefins, e.g. butylene, isobutylene,
diisobutene, styrene and .alpha.-methylstyrene, and also diolefins
with an active double bond, e.g. butadiene; [0071] (g) unsaturated
nitriles, such as acrylonitrile and methacrylonitrile.
[0072] A preferred monomer D is selected from methyl
(meth)acrylate, ethyl (meth)acrylate, (meth)acrylamide, vinyl
acetate, vinyl propionate, vinyl methyl ether, N-vinylformamide,
N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam.
N-vinylimidazol is particularly preferred.
[0073] If the monomer D is present in the copolymer of the present
invention, then the proportion of monomer D may be up to 40%,
preferably from 1% to 30%, more preferably from 5% to 20% by weight
of the copolymer.
[0074] Preferred copolymers of the present invention include:
##STR00003##
wherein indices y and z are such that the monomer ratio (z:y) is
from 3:1 to 20:1 and the inidces x and z are such that the monomer
ratio (z:x) is from 1.5:1 to 20:1, and the polymer has a weight
average molecular weight of from 20,000 to 500,000 g/mol,
preferably from greater than 25,000 to 150,000 g/mol and especially
from 30,000 to 80,000 g/mol.
[0075] The copolymers according to the invention can be prepared by
free-radical polymerization of the Monomers A and B and if desired
C and/or D. The free-radical polymerization of the monomers can be
carried out in accordance with all known methods, preference being
given to the processes of solution polymerization and of emulsion
polymerization. Suitable polymerization initiators are compounds
which decompose thermally or photochemically (photoinitiators) to
form free radicals, such as benzophenone, acetophenone, benzoin
ether, benzyl dialkyl ketones and derivatives thereof.
[0076] The polymerization initiators are used according to the
requirements of the material to be polymerized, usually in amounts
of from 0.01% to 15%, preferably 0.5% to 5% by weight based on the
monomers to be polymerized, and can be used individually or in
combination with one another.
[0077] Instead of a quaternized Monomer B, it is also possible to
use the corresponding tertiary amines In this case, the
quaternization is carried out after the polymerization by reacting
the resulting copolymer with alkylating agents, such as alkyl
halides, dialkyl sulfates and dialkyl carbonates, or benzyl
halides, such as benzyl chloride. Examples of suitable alkylating
agents which may be mentioned are, methyl chloride, bromide and
iodide, ethyl chloride and bromide, dimethyl sulfate, diethyl
sulfate, dimethyl carbonate and diethyl carbonate.
[0078] The anionic monomer C can be used in the polymerization
either in the form of the free acids or in a form partially or
completely neutralized with bases. Specific examples that may be
listed are: sodium hydroxide solution, potassium hydroxide
solution, sodium carbonate, sodium hydrogen carbonate,
ethanolamine, diethanolamine and triethanolamine
[0079] To limit the molar masses of the copolymers according to the
invention, customary regulators can be added during the
polymerization, e.g. mercapto compounds, such as mercaptoethanol,
thioglycolic acid and sodium disulfite. Suitable amounts of
regulator are 0.1% to 5% by weight based on the monomers to be
polymerized.
[0080] Optional Ingredients
[0081] The compositions according to the present invention may
comprise a variety of optional ingredients depending on the
technical benefit aimed for and the surface treated.
[0082] Suitable optional ingredients for use herein include other
acids, preferably acetic acid and/or lactic acid and/or citric
acid, chelating agents, nonionic surfactants, vinylpyrrolidone
homopolymer or copolymer, polysaccharide polymer, radical
scavengers, perfumes, solvents, other surfactants, builders,
buffers, bactericides, hydrotropes, colorants, stabilizers,
bleaches, bleach activators, suds controlling agents like fatty
acids, enzymes, soil suspenders, brighteners, anti dusting agents,
dispersants, pigments, and dyes.
[0083] Nonionic Surfactant
[0084] The compositions of the present invention preferably
comprise a nonionic surfactant, or a mixture thereof. This class of
surfactants may be desired as it further contributes to cleaning
performance of the hard surface cleaning compositions herein. It
has been found in particular that nonionic surfactants strongly
contribute in achieving highly improved performance on greasy soap
scum removal.
[0085] The compositions according to the present invention may
comprise up to 15% by weight of the total composition of a nonionic
surfactant or a mixture thereof, preferably from 0.1% to 10%, more
preferably from 0.5% to 5%, even more preferably from 1.0% to 3% by
weight of the total composition.
[0086] Suitable nonionic surfactants for use herein are alkoxylated
alcohol nonionic surfactants, which can be readily made by
condensation processes which are well-known in the art. However, a
great variety of such alkoxylated alcohols, especially ethoxylated
and/or propoxylated alcohols, is conveniently commercially
available. Surfactants catalogs are available which list a number
of surfactants, including nonionics.
[0087] Accordingly, preferred alkoxylated alcohols for use herein
are nonionic surfactants according to the formula RO(E)e(P)pH where
R is a hydrocarbon chain of from 2 to 24 carbon atoms, E is
ethylene oxide and P is propylene oxide, and e and p which
represent the average degree of, respectively ethoxylation and
propoxylation, are of from 0 to 24 (with the sum of e+p being at
least 1). Preferably, the hydrophobic moiety of the nonionic
compound can be a primary or secondary, straight or branched
alcohol having from 8 to 24 carbon atoms.
[0088] Preferred nonionic surfactants for use in the compositions
according to the invention are the condensation product of ethylene
and/or propylene oxide with an alcohol having a straight alkyl
chain comprising from 6 to 22 carbon atoms, wherein the degree of
ethoxylation/propoxylation is from 1 to 15, preferably from 5 to 12
or mixtures thereof. Such suitable nonionic surfactants are
commercially available from Shell, for instance, under the trade
name Neodol.RTM. or from BASF under the trade name
Lutensol.RTM..
[0089] Anionic Polymeric Thickeners
[0090] Surprisingly, anionic polymeric thickeners can be used to
achieve the desired composition viscosity, even though the
copolymers comprise cationic monomeric units (monomer B).
[0091] Preferred anionic polymeric thickeners are polysaccharide
polymers. As such, the compositions of the present invention may
optionally comprise a polysaccharide polymer or a mixture thereof.
Typically, the compositions of the present invention may comprise
from 0.01% to 5% by weight of the total composition of a
polysaccharide polymer or a mixture thereof, more preferably from
0.05% to 3% and most preferably from 0.05% to 1%.
[0092] Suitable polysaccharide polymers for use herein include
substituted cellulose materials like carboxymethylcellulose, ethyl
cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,
hydroxymethyl cellulose, succinoglycan and naturally occurring
polysaccharide polymers like Xanthan gum, gellan gum, guar gum,
locust bean gum, tragacanth gum or derivatives thereof, or mixtures
thereof.
[0093] In a preferred embodiment according to the present invention
the compositions of the present invention comprise a polysaccharide
polymer selected from the group consisting of:
carboxymethylcellulose, ethyl cellulose, hydroxyethyl cellulose,
hydroxypropyl cellulose, hydroxymethyl cellulose, succinoglycan
gum, xanthan gum, gellan gum, guar gum, locust bean gum, tragacanth
gum, derivatives of the aforementioned, and mixtures thereof.
Preferably, the compositions herein comprise a polysaccharide
polymer selected from the group consisting of: succinoglycan gum,
xanthan gum, gellan gum, guar gum, locust bean gum, tragacanth gum,
derivatives of the aforementioned, and mixtures thereof. More
preferably, the compositions herein comprise a polysaccharide
polymer selected from the group consisting of: xanthan gum, gellan
gum, guar gum, derivatives of the aforementioned, and mixtures
thereof. Most preferably, the compositions herein comprise xanthan
gum, derivatives thereof, or mixtures thereof.
[0094] Particularly polysaccharide polymers for use herein are
xanthan gum and derivatives thereof. xanthan gum and derivatives
thereof may be commercially available for instance from CP Kelco
under the trade name Keltrol RD.RTM., Kelzan S.RTM. or Kelzan
T.RTM.. Other suitable xanthan gums are commercially available by
Rhodia under the trade name Rhodopol T.RTM. and Rhodigel X747.RTM..
Succinoglycan gum for use herein is commercially available by
Rhodia under the trade name Rheozan.RTM..
[0095] It has been surprisingly found that composition comprising
the copolymers described herein, when added into an aqueous acidic
composition deliver faster drying when treating a surface as well
as improving the stability of the compositions, while delivering
good first-time hard-surface cleaning performance and good
limescale removal performance.
[0096] The composition of the invention may comprise additional
cleaning ingredients.
[0097] Vinylpyrrolidone Homopolymer or Copolymer
[0098] In order to provide improved shine over a wider range of
surfaces, the compositions of the present invention may comprise a
vinylpyrrolidone homopolymer or copolymer, or a mixture thereof.
Typically, the compositions of the present invention may comprise
from 0.01% to 5% by weight of the total composition of a
vinylpyrrolidone homopolymer or copolymer, or a mixture thereof,
more preferably from 0.05% to 3% and most preferably from 0.05% to
1%.
[0099] Suitable vinylpyrrolidone homopolymers for use herein are
homopolymers of N-vinylpyrrolidone having the following repeating
monomer:
##STR00004##
wherein n (degree of polymerisation) is an integer of from 10 to
1,000,000, preferably from 20 to 100,000, and more preferably from
20 to 10,000.
[0100] Accordingly, suitable vinylpyrrolidone homopolymers ("PVP")
for use herein have an average molecular weight of from 1,000 to
100,000,000, preferably from 2,000 to 10,000,000, more preferably
from 5,000 to 1,000,000, and most preferably from 50,000 to
500,000.
[0101] Suitable vinylpyrrolidone homopolymers are commercially
available from ISP Corporation, New York, N.Y. and Montreal, Canada
under the product names PVP K-15.RTM. (viscosity molecular weight
of 10,000), PVP K-30.RTM. (average molecular weight of 40,000), PVP
K-60.RTM. (average molecular weight of 160,000), and PVP K-90.RTM.
(average molecular weight of 360,000). Other suitable
vinylpyrrolidone homopolymers which are commercially available from
BASF Cooperation include Sokalan HP 165.RTM., Sokalan HP 12.RTM.,
Luviskol K30.RTM., Luviskol K60.RTM., Luviskol K80.RTM., Luviskol
K90.RTM.; vinylpyrrolidone homopolymers known to persons skilled in
the detergent field (see for example EP-A-262,897 and
EP-A-256,696).
[0102] Suitable copolymers of vinylpyrrolidone for use herein
include copolymers of N-vinylpyrrolidone and alkylenically
unsaturated monomers or mixtures thereof.
[0103] The alkylenically unsaturated monomers of the copolymers
herein include unsaturated dicarboxylic acids such as maleic acid,
chloromaleic acid, fumaric acid, itaconic acid, citraconic acid,
phenylmaleic acid, aconitic acid, acrylic acid, N-vinylimidazole
and vinyl acetate. Any of the anhydrides of the unsaturated acids
may be employed, for example acrylate, methacrylate. Aromatic
monomers like styrene, sulphonated styrene, alpha-methyl styrene,
vinyl toluene, t-butyl styrene and similar well known monomers may
be used.
[0104] For example particularly suitable N-vinylimidazole
N-vinylpyrrolidone polymers for use herein have an average
molecular weight range from 5,000 to 1,000,000, preferably from
5,000 to 500,000, and more preferably from 10,000 to 200,000. The
average molecular weight range was determined by light scattering
as described in Barth H. G. and Mays J. W. Chemical Analysis Vol
113,"Modern Methods of Polymer Characterization".
[0105] Such copolymers of N-vinylpyrrolidone and alkylenically
unsaturated monomers like PVP/vinyl acetate copolymers are
commercially available under the trade name Luviskol.RTM. series
from BASF.
[0106] According to a very preferred execution of the present
invention, vinylpyrrolidone homopolymers are advantageously
selected.
[0107] Chelating Agent
[0108] The compositions of the present invention may comprise a
chelating agent or mixtures thereof, as a preferred optional
ingredient. Chelating agents can be incorporated in the
compositions herein in amounts ranging from 0% to 10% by weight of
the total composition, preferably 0.01% to 5.0%, more preferably
0.05% to 1%.
[0109] Suitable phosphonate chelating agents to be used herein may
include alkali metal ethane 1-hydroxy diphosphonates (HEDP),
alkylene poly (alkylene phosphonate), as well as amino phosphonate
compounds, including amino aminotri(methylene phosphonic acid)
(ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine
tetra methylene phosphonates, and diethylene triamine penta
methylene phosphonates (DTPMP). The phosphonate compounds may be
present either in their acid form or as salts of different cations
on some or all of their acid functionalities.
[0110] Preferred chelating agents to be used herein are diethylene
triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy
diphosphonate (HEDP). In a particularly preferred execution of the
present invention, the chelating agent is selected to be ethane
1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents
are commercially available from Monsanto under the trade name
DEQUEST.RTM..
[0111] Polyfunctionally-substituted aromatic chelating agents may
also be useful in the compositions herein. See U.S. Pat. No.
3,812,044, issued May 21, 1974, to Connor et al. Preferred
compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-dihydroxy -3,5-disulfobenzene. A preferred
biodegradable chelating agent for use herein is ethylene diamine
N,N'-disuccinic acid, or alkali metal, or alkaline earth, ammonium
or substitutes ammonium salts thereof or mixtures thereof.
Ethylenediamine N,N'-disuccinic acids, especially the (S,S) isomer
have been extensively described in U.S. Pat. No. 4, 704, 233, Nov.
3, 1987, to Hartman and Perkins. Ethylenediamine N,N'-disuccinic
acids is, for instance, commercially available under the tradename
ssEDDS.RTM. from Palmer Research Laboratories.
[0112] Suitable amino carboxylates to be used herein include tetra
sodium glutamate diacetate (GLDA), ethylene diamine tetra acetates,
diethylene triamine pentaacetates, diethylene triamine pentaacetate
(DTPA), N-hydroxyethylethylenediamine triacetates,
nitrilotri-acetates, ethylenediamine tetrapropionates,
triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene
diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid
(MGDA), both in their acid form, or in their alkali metal,
ammonium, and substituted ammonium salt forms. Particularly
suitable amino carboxylates to be used herein are diethylene
triamine penta acetic acid, propylene diamine tetracetic acid
(PDTA) which is, for instance, commercially available from BASF
under the trade name Trilon FS.RTM. methyl glycine di-acetic acid
(MGDA), tetra sodium glutamate diacetate (GLDA) which is, for
instance, commercially available from AkzoNobel under the trade
name Dissolvine.RTM. GL.
[0113] Further carboxylate chelating agents to be used herein
include salicylic acid, aspartic acid, glutamic acid, glycine,
malonic acid or mixtures thereof.
[0114] The addition of a chelating agent, preferably HEDP, in the
composition of the present invention provides an unexpected
improvement in terms of limescale removal.
[0115] Solvent
[0116] The compositions of the present invention may further
comprise a solvent or a mixture thereof, as an optional ingredient.
Solvents to be used herein include all those known to those skilled
in the art of hard-surfaces cleaner compositions. In a highly
preferred embodiment, the compositions herein comprise an
alkoxylated glycol ether (such as n-Butoxy Propoxy Propanol
(n-BPP)) or a mixture thereof.
[0117] Typically, the compositions of the present invention may
comprise from 0.1% to 5% by weight of the total composition of a
solvent or mixtures thereof, preferably from 0.5% to 5% by weight
of the total composition and more preferably from 1% to 3% by
weight of the total composition.
[0118] Additional Surfactant
[0119] The compositions of the present invention may comprise an
additional surfactant, or mixtures thereof, on top of the nonionic
surfactant already described herein. Additional surfactants may be
desired herein as they further contribute to the cleaning
performance and/or shine benefit of the compositions of the present
invention. Surfactants to be used herein include anionic
surfactants, cationic surfactants, amphoteric surfactants,
zwitterionic surfactants, and mixtures thereof. Accordingly, the
compositions according to the present invention may comprise up to
15% by weight of the total composition of another surfactant or a
mixture thereof, on top of the nonionic surfactant already
described herein, more preferably from 0.5% to 5%, even more
preferably from 0.5% to 3%, and most preferably from 0.5% to 2%.
Different surfactants may be used in the present invention
including anionic, cationic, zwitterionic or amphoteric
surfactants. It is also possible to use mixtures of such
surfactants without departing from the spirit of the present
invention.
[0120] Preferred surfactants for use herein are anionic and
zwitterionic surfactants since they provide excellent grease soap
scum cleaning ability to the compositions of the present
invention.
[0121] Anionic surfactants may be included herein as they
contribute to the cleaning benefits of the hard-surface cleaning
compositions of the present invention. Indeed, the presence of an
anionic surfactant contributes to the greasy soap scum cleaning of
the compositions herein. More generally, the presence of an anionic
surfactant in the liquid acidic compositions according to the
present invention allows to lower the surface tension and to
improve the wettability of the surfaces being treated with the
liquid acidic compositions of the present invention. Furthermore,
the anionic surfactant, or a mixture thereof, helps to solubilize
the soils in the compositions of the present invention.
[0122] Suitable anionic surfactants for use herein are all those
commonly known by those skilled in the art. Preferably, the anionic
surfactants for use herein include alkyl sulphonates, alkyl aryl
sulphonates, or mixtures thereof.
[0123] Particularly suitable linear alkyl sulphonates include C8
sulphonate like Witconate.RTM. NAS 8 commercially available from
Witco.
[0124] Other anionic surfactants useful herein include salts
(including, for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and triethanolamine
salts) of soap, alkyl sulphates, alkyl aryl sulphates alkyl
alkoxylated sulphates, C8-C24 olefinsulfonates, sulphonated
polycarboxylic acids prepared by sulphonation of the pyrolyzed
product of alkaline earth metal citrates, e.g., as described in
British patent specification No. 1,082,179; alkyl ester sulfonates
such as C14-16 methyl ester sulfonates; acyl glycerol sulfonates,
alkyl phosphates, isethionates such as the acyl isethionates,
N-acyl taurates, alkyl succinamates, acyl sarcosinates, sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside
(the nonionic nonsulfated compounds being described below), alkyl
polyethoxy carboxylates such as those of the formula
RO(CH2CH2O)kCH2COO-M+ wherein R is a C8-C22 alkyl, k is an integer
from 0 to 10, and M is a soluble salt-forming cation. Resin acids
and hydrogenated resin acids are also suitable, such as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids
present in or derived from tall oil. Further examples are given in
"Surface Active Agents and Detergents" (Vol. I and II by Schwartz,
Perry and Berch). A variety of such surfactants are also generally
disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to
Laughlin, et al. at Column 23, line 58 through Column 29, line
23.
[0125] Suitable zwitterionic surfactants for use herein contain
both basic and acidic groups which form an inner salt giving both
cationic and anionic hydrophilic groups on the same molecule at a
relatively wide range of pH's. The typical cationic group is a
quaternary ammonium group, although other positively charged groups
like phosphonium, imidazolium and sulfonium groups can be used. The
typical anionic hydrophilic groups are carboxylates and sulfonates,
although other groups like sulfates, phosphonates, and the like can
be used.
[0126] Some common examples of zwitterionic surfactants (i.e.
betaine/sulphobetaine) are described in U.S. Pat. Nos. 2,082,275,
2,702,279 and 2,255,082.
[0127] For example Coconut dimethyl betaine is commercially
available from Seppic under the trade name of Amonyl 265.RTM..
Lauryl betaine is commercially available from Albright & Wilson
under the trade name Empigen BB/L.RTM.. A further example of
betaine is Lauryl-immino-dipropionate commercially available from
Rhodia under the trade name Mirataine H2C-HA.RTM..
[0128] Particularly preferred zwitterionic surfactants for use in
the compositions of the present invention are the sulfobetaine
surfactants as they deliver optimum soap scum cleaning
benefits.
[0129] Examples of particularly suitable sulfobetaine surfactants
include tallow bis(hydroxyethyl) sulphobetaine, cocoamido propyl
hydroxy sulphobetaines which are commercially available from Rhodia
and Witco, under the trade name of Mirataine CBS.RTM. and Rewoteric
AM CAS 15.RTM. respectively.
[0130] Amphoteric and ampholytic detergents which can be either
cationic or anionic depending upon the pH of the system are
represented by detergents such as dodecylbeta-alanine,
N-alkyltaurines such as the one prepared by reacting dodecylamine
with sodium isethionate according to the teaching of U.S. Pat. No.
2,658,072, N-higher alkylaspartic acids such as those produced
according to the teaching of U.S. Pat. No. 2,438,091, and the
products sold under the trade name "Miranol", and described in U.S.
Pat. No. 2,528,378. Additional synthetic detergents and listings of
their commercial sources can be found in McCutcheon's Detergents
and Emulsifiers, North American Ed. 1980.
[0131] Suitable amphoteric surfactants include the amine oxides.
Examples of amine oxides for use herein are for instance coconut
dimethyl amine oxides, C12-C16 dimethyl amine oxides. Said amine
oxides may be commercially available from Clariant, Stepan, and
AKZO (under the trade name Aromox.RTM.). Other suitable amphoteric
surfactants for the purpose of the invention are the phosphine or
sulfoxide surfactants.
[0132] Cationic surfactants suitable for use in compositions of the
present invention are those having a long-chain hydrocarbyl group.
Examples of such cationic surfactants include the quaternary
ammonium surfactants such as alkyldimethylammonium halogenides.
Other cationic surfactants useful herein are also described in U.S.
Pat. No. 4,228,044, Cambre, issued Oct. 14, 1980.
[0133] The Process of Cleaning a Hard-Surface or an Object
[0134] The copolymers, described herein, can be used in an acidic
composition for reducing drying time on a hard surface while
improving the shine and phase stability of the composition.
[0135] The present invention further encompasses a process of
cleaning a hard surface or an object, preferably removing limescale
from said hard-surface or said object with a reduced drying time.
The process according to the present invention comprises the steps
of: applying the liquid acidic hard surface cleaning composition
onto said hard-surface or said object; leaving said composition on
said hard-surface or said object to act; optionally wiping said
hard-surface or object and/or providing mechanical agitation, and
then rinsing said hard-surface or said object.
[0136] By "hard-surface", it is meant herein any kind of surfaces
typically found in and around houses like bathrooms, kitchens,
basements and garages, e.g., floors, walls, tiles, windows, sinks,
showers, shower plastified curtains, wash basins, WCs, dishes,
fixtures and fittings and the like made of different materials like
ceramic, enamel, painted and un-painted concrete, plaster, bricks,
vinyl, no-wax vinyl, linoleum, melamine, Formica.RTM., glass, any
plastics, metals, chromed surface and the like. The term surfaces
as used herein also include household appliances including, but not
limited to, washing machines, automatic dryers, refrigerators,
freezers, ovens, microwave ovens, dishwashers and so on. Preferred
hard surfaces cleaned with the liquid aqueous acidic hard surface
cleaning composition herein are those located in a bathroom, in a
toilet or in a kitchen, basements, garages as well as outdoor such
as garden furniture, gardening equipments, driveways etc.
[0137] The objects herein are objects that are subjected to
limescale formation thereon. Such objects may be water-taps or
parts thereof, water-valves, metal objects, objects made of
stainless-steel, cutlery and the like.
[0138] The copolymers described herein are particularly useful in
acidic cleaning compositions for providing a reduced drying time on
surfaces, while also not affecting limescale removal.
[0139] The preferred process of cleaning a hard-surface or an
object (preferably removing limescale from said hard-surface or
said object) comprises the step of applying a composition according
to the present invention onto said hard-surface or object, leaving
said composition on said hard-surface or object to act, preferably
for an effective amount of time, more preferably for a period
comprised between 10 seconds and 10 minutes, most preferably for a
period comprised between 15 seconds and 4 minutes; optionally
wiping said hard-surface or object with an appropriate instrument,
e.g. a sponge; and then preferably rinsing said surface with
water.
[0140] Even though said hard-surface or object may optionally be
wiped and/or agitated during the process herein, it has been
surprisingly found that the process of the present invention allows
good limescale removal performance without any additional
mechanical wiping and/or agitation action. The lack of need for
additional wiping and/or mechanical; agitation provides an added
convenience for the user of the compositions herein.
[0141] The compositions of the present invention may be contacted
to the surface or the object to be treated in its neat form or in
its diluted form. Preferably, the composition is applied in its
neat form.
[0142] By "diluted form", it is meant herein that said composition
is diluted by the user, typically with water. The composition is
diluted prior use to a typical dilution level of 10 to 400 times
its weight of water, preferably from 10 to 200 and more preferably
from 10 to 100. Usual recommended dilution level is a 1.2% dilution
of the composition in water.
[0143] The compositions according to the present invention are
particularly suitable for treating hard-surfaces located in and
around the house, such as in bathrooms, toilets, garages, on
driveways, basements, gardens, kitchens, etc., and preferably in
bathrooms. It is however known that such surfaces (especially
bathroom surfaces) may be soiled by the so-called
"limescale-containing soils". By "limescale-containing soils" it is
meant herein any soil which contains not only limescale mineral
deposits, such as calcium and/or magnesium carbonate, but also soap
scum (e.g., calcium stearate) and other grease (e.g. body grease).
By "limescale deposits" it is mean herein any pure limescale soil,
i.e., any soil or stains composed essentially of mineral deposits,
such as calcium and/or magnesium carbonate.
[0144] The compositions herein may be packaged in any suitable
container, such as bottles, preferably plastic bottles, optionally
equipped with an electrical or manual trigger spray-head.
[0145] Polymer Synthesis
[0146] GPC(SEC) Method to determine the molecular weight of the
copolymer:
[0147] The weight average molecular weight of the polymers are
determined by the technique of Size Exclusion Chromatography (SEC).
SEC separation conditions were three hydrophilic Vinylpolymer
network gel columns, in distilled water ion the presence of 0,1%
(w/w) trifluoroacetic acid/0,1 M NaCl at 35.degree. C. Calibration
was done with narrowly distributed Poly(2-vinylpyridine)-standard
of company PSS, Deutschland with molecular weights Mw=620 to
M=2.070.000.
[0148] Example polymer according to the invention: MPEG-EO
units/Vinyl imidazole/Methyl-vinyl-imidazolium, 80/15/5wt %.
[0149] In a 2 L stirred vessel, water (199 g) was charged and
heated to 85.degree. C. under a flow of nitrogen. A solution of
Wako V50 (3 g, Wako Pure Chemical Industries, Ltd.) in water (47 g)
is added over 4 h, a solution of Methoxypolyethylenglycol
methacrylate with molecular weight.about.1000 g/mol (50%, 484,8 g,
Bisiomer S10W, GEO Specialty Chemicals) and
3-Methyl-1-vinyl-1H-imidazolium-methyl-sulfat (45%, 33,3 g, BASF
SE), and 1-vinylimidazole (45 g) and water (177,6 g) over 3 hours.
The polymerization mixture is kept at this temperature for
additional 30 min after the three streams have finished.
Subsequently a solution of Wako V50 (1,5 g) in water (23,5 g) is
added at once and the reaction stirred for 2 h. Afterwards the
reaction cooled down to room temperature. The GPC measured
following above method gives values of Mw=60,300 g/mol.
[0150] Methods:
[0151] A) pH Measurement:
[0152] The pH is measured on the neat composition, at 25.degree.
C., using a Sartarius PT-10P pH meter with gel-filled probe (such
as the Toledo probe, part number 52 000 100), calibrated according
to the instructions manual.
EXAMPLE 1
[0153] These following compositions were made comprising the listed
ingredients in the listed proportions (active weight %). The
examples herein are met to exemplify the present invention but are
not necessarily used to limit or otherwise define the scope of the
present invention.
[0154] To illustrate the shorter drying times obtained with the
compositions of the invention, the protocol below was followed. Two
compositions were prepared, compositions A according to the
invention and composition B as a reference composition outside the
scope of the invention. The values are reported as percent of
active raw material.
TABLE-US-00001 Composition A According to the B invention Reference
composition % of active raw material Water Balance up to 100
Balance up to 100 Citric acid 4.20 4.20 Formic acid 2.70 2.70
Nonionic surfactant .sup.1 2.20 2.20 Sodium Hydroxide 0.50 0.50
Xantham gum 0.30 0.30 Perfume 0.24 0.24 Aesthetic dye 0.10 0.10
Polyvinylpyrrolidone -- 0.025 Polymer A .sup.2 0.025 -- pH 1.98
1.98 .sup.1 Non-ionic surfactant is C9-C11 8EO, sourced as Neodol
.RTM. 91-8 from Shell. .sup.2 Polymer A is MPEG-25EO/QVI/VI with a
80/5/15 percent weight and 60,300 g/mol
[0155] The drying test is done on a standard test surface, which is
a black glossy tile (Sphinx Highlight Black, 20 cm.times.20 cm,
available from Carobati Boomsesteenweg 36, 2630 Aartselaar,
Blegium). The black tiles are washed with an all-purpose cleaner,
not containing any polymer (Mr. Propre APC, commercially available)
and thoroughly rinse with tap water until they are completely free
of any residue. The tiles are then dried with a paper towel. The
tiles are then placed vertically (with a slight inclination of up
to 5 degrees) resting on a suitable support.
[0156] With a plastic disposable pipette, 3 mL of the solution are
then applied at the top of the tile with a swift motion from the
top left to the top right corner. The product is then immediately
spread evenly across the surface of the tile, with at least four
vertical strokes followed by four horizontal strokes using a
cellulose sponge. (The sponges have been washed at 95 C three times
in a domestic washing machine, without any detergent, prior to the
experiment). The product is allowed to remain on the surface for 15
seconds.
[0157] Once this time has passed, the tiles are then thoroughly
rinsed for 30 seconds using a showerhead with a water flow of 4
L/min. The tiles are then allowed to dry, measuring the time it
takes for the water to evaporate. Once the tiles are dry the shine
of the tiles washed with the composition of the invention is
compared to the shine of the tile washed with the reference
composition. A visual grading system is used, going from 0 to 5,
where 0 means perfect sparkling and clear surface and 5 means
cloudy surface with visible streaks and water marks. The tiles are
dried in a controlled temperature and humidity room at 20.degree.
C. and a relative humidity of 40%. The procedure is repeated twice
and the average values reported.
TABLE-US-00002 Shine visual grades Testing product Water Drying
time (sec) (absolute) Composition B 130 4 Composition A 11 1.4
[0158] From this example is possible to see that the composition
containing the copolymer of the present invention has a shorter
drying time and an improved shine after rinsing the product from
the tile.
EXAMPLE 2
[0159] The following five compositions were prepared to illustrate
the benefits of the invention. Compositions C, D, E and F contain a
copolymer as defined by the present invention, while composition G
is outside of the scope of the invention and is used a comparative
example.
TABLE-US-00003 Composition G C D E F Reference According to the
invention composition Ingredient % of active raw material Water
Balance Balance Balance Balance Balance up up up up up to 100 to
100 to 100 to 100 to 100 Formic acid 2.70 2.70 2.70 2.70 2.70
Nonionic 2.20 2.20 2.20 2.20 2.20 surfactant .sup.1 Citric acid
1.70 1.70 1.70 1.70 1.70 Sodium 0.50 0.50 0.50 0.50 0.50 Hydroxide
Xantham gum 0.30 0.30 0.30 0.30 0.30 Polyvinyl- -- -- -- -- 0.025
pyrrolidone Polymer A .sup.2 0.025 -- -- -- -- Polymer B .sup.3 --
0.025 -- -- -- Polymer C .sup.4 -- -- 0.025 -- -- Polymer D .sup.5
-- -- -- 0.025 -- pH 2.2 2.2 2.2 2.2 2.2 .sup.1 Non-ionic
surfactant is C9-C10 EO8, sourced as Marlipal .RTM.. .sup.2 Polymer
A is MPEG-25EO/QVI/VI with a 80/5/15 percent weight and 60,300
g/mol .sup.3 Polymer B is MPEG-25EO/QVI/VI with a 80/10/10 percent
weight and 79,200 g/mol .sup.4 Polymer C is MPEG-25EO/QVI with a
80/20 percent weight and 34,100/mol .sup.5 Polymer D is
MPEG-25EO/QVI/VI with a 90/5/5 percent weight and 52,425 g/mol
[0160] Following the methodology described above the following
drying times and shine grades where recorded.
TABLE-US-00004 Shine visual grades Testing product Water Drying
time (sec) (absolute) Composition G 115 2.5 Composition F 9 2.75
Composition E 13 2.25 Composition D 13 1.38 Composition C 26
1.75
[0161] As in the previous example, compositions containing the
copolymer of the inventions exhibit a faster drying after once
rinse once the product is applied to the surface.
[0162] The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm. "
[0163] Every document cited herein, including any cross referenced
or related patent or application and any patent application or
patent to which this application claims priority or benefit
thereof, is hereby incorporated herein by reference in its entirety
unless expressly excluded or otherwise limited. The citation of any
document is not an admission that it is prior art with respect to
any invention disclosed or claimed herein or that it alone, or in
any combination with any other reference or references, teaches,
suggests or discloses any such invention. Further, to the extent
that any meaning or definition of a term in this document conflicts
with any meaning or definition of the same term in a document
incorporated by reference, the meaning or definition assigned to
that term in this document shall govern.
[0164] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
* * * * *